3,095,356 United States Patent Office Patented June 25, 1963

1. 2 3,095,356 of uptake by the teeth. Soluble are DENTIFRICE COMPRISING INSOLUBLE SODIUM found to be taken up to a greater extent when these metal METAPHOSPHATE AND A CADMUM, TN, saits are also present with the fluoride. The proportion , MANGANESE OR IRON COMPOUND TO of the fluorides, such as aluminum, tin, or INHIBIT CALCUM ON SEQUESTERNG employed in the practice of the present invention is in the Henry V. Moss, Clayton, Mo, assignor to Monsanto range of 0.05 to 1% by weight of the dentifrice composi Chemical Company, St. Louis, Mo., a corporation of tion. However, the total proportion of metal compounds Delaware w of the group of cadmium, tin, zinc, manganese, alumi No Drawing. Filed Feb. 20, 1956, Ser. No. 566,353 num and iron which are present in the dentifrice is within 11 Claims. (CI. 167-93) 10 the broader range of 0.05 to 50 weight percent. This invention relates to polishing compositions suitable According to one of the present theories as to the for use as a dentifrice base and particularly to those com molecular aggregation of phosphate salts, the insoluble positions which contain the insoluble form of sodium sodium metaphosphate containing the usual impurities, metaphosphate as an ingredient thereof. may exist as a chain-type of molecular structure, and also An object of the present invention is the provision of 5 in the form of relatively short-chain polyphosphates. Ac an improved identifice. - cording to this theory, the presently employed metal com The use of the so-called insoluble form of sodium pounds control the sequestering action of polyphosphates, metaphosphate in finely divided form has been proposed thereby controlling the type of molecular structures pre as a dentifrice. This material, however, has a definite, sent in an aqueous solution or dispersion in which the though small, solubility in water or other aqueous liquids. 20 said insoluble sodium metaphosphate may be present. Further, it has been found that the soluble part of the However, the above discussion is not necessarily a com so-called “insoluble' metaphosphate has a definite solubi plete explanation of the mode of action of the presently lizing action on certain lime salts. employed metal compounds, for example, and the present I have now found that by incorporating small amounts invention is not restricted thereto. of compounds of cadmium, tin, zinc, manganese, alumi 25 The invention in general contemplates the use of finely num and iron, particularly those of aluminum and Zinc, divided insoluble sodium metaphosphate as a component which furnish available dissolved aluminum or zinc , of a dentifrice base. The combination also includes a it becomes possible to inhibit the dissolving action of the sufficient amount of the above compound of a metal se “soluble" portion of the insoluble form of sodium meta lected from the group consisting of cadmium, tin, zinc, phosphate. 30 manganese, aluminum, and iron to inhibit the calcium The specific metal compounds which I may add to the sequestering effect, characteristic of the said sodium meta insoluble sodium metaphosphate may either be soluble phosphate. A preferred group of compounds utilized for or insoluble in water or related aqueous solutions. Exam such inhibition are the compounds of aluminum and zinc, ples of suitable salts, representative of all of the above a still more preferred embodiment being aluminum hy class, but exemplified specifically with respect to the alu 35 drate, i.e., Al(OH)3. This compound which is also known minum and are the oxides Al2O3 or ZnO, as aluminum hydroxide is employed in the present denti or hydrated oxides AlO3H2O, the chlorides AlCl3 or frice composition. It is also found that this compound ZnCl2, the sulfates Al2(SO4)3, or ZnSO4, the citrates provides a secondary advantage in dentifrice compositions, AICHO, or Zn3(C6H5O)2, the phosphates such as the inasmuch as the aluminum hydrate provides a highly de orthophosphates AlPO, or Zn3(PO4)2, etc. Other molec 40 sirable whitening effect which improves the tinctorial pow ular forms and various hydrated compounds may also be er and opacity of the toothpaste. - employed. These additive materials may be incorporated The above-described inhibiting compositions utilized in the proportion of 0.05% to 50% by weight as a slurry together with the insoluble sodium metaphosphate are or dry powder with the insoluble metaphosphate for in also of great utility in combination with various fluorides corporation into a tooth powder or tooth paste. The 45 which are employed in many dentifrice compositions. It proportion of such metal salts is not critical, and hence, has been a disadvantage of many polishing agents con may be varied in order to furnish the desired inhibiting ventionally employed in dentifrices that certain polishing action. . agents are incompatible with fluorides. For example, Particularly useful salts in this relationship are the calcium compounds readily precipitate the highly insolu fluorides of cadmium, tin, zinc, manganese, aluminum and 50 ble calcium fluoride which thus prevents the fluoride iron, a preferred group being aluminum fluoride, AlF3, ion from being effective in the use of such toothpowders or zinc fluoride, Zn,F2. These fluorides concomitantly and toothpastes containing the same. The use of the provide an agent effective in reducing the sequestering presently described metal compounds, for example alumi action of the soluble portion of the sodium metaphosphate, num hydrate as described above, in combination with while also providing fluoride in a form which is useful in 55 insoluble sodium metaphosphate, completely eliminates formulated dentifrices. All of the fluoride compounds the possibility of precipitating fluoride ions which may be described above are effective in reducing the sequestering present in combination with these two components. Ac action of insoluble sodium metaphosphate. - cordingly, the combination of the sodium metaphosphate If a fluoride type dentifrice is desired, a soluble fluoride and aluminum hydrate provides a highly efficacious den salt may be used, for example stannous fluoride employed 60 tifrice base which may be formulated with conventional at about 0.1 weight percent, calculated as fluoride. In fluoride compounds. With regard to the other compounds general the weight percentage of the fluoride, including described above, the following fluorides exhibit substan the preferred group of aluminum fluoride, stannous tial solubility in a precipitating system such as a tooth fluoride and sodium fluoride, present as the salt, is in the paste, so that precipitation and consequent loss of the range of 0.5% to 1%. : 65 fluoride is avoided: , stannous fluoride, An advantage of the present use of fluorides with the Zinc fluoride, manganous fluoride, aluminum fluoride, above-described group of metal salts is the improvement ferrous fluoride, and ferric fluoride. 3,095,856 3 4. Soluble calcium salts and insoluble calcium orthophos The detergents employed, in general, are of the alkyl phates, as set forth above, are undesirable in fluoride sulfate type. However non-soap synthetic detergents are dentifrices because of reaction with the fluoride to pro of utility in this relationship in the present invention to duce insoluble calcium fluoride or fluorapatite which provide a non-soap wetting and foaming agent in the renders the fluoride content unavailable to the teeth. 5 dentifrice. Similar disadvantages are found to arise in the use of The toothpaste was prepared by combining 450 parts by magnesium compounds. Furthermore, the use of mag weight of powder prepared according to the above formu nesium compounds in the presence of insoluble sodium lation with 550 parts of an elixir prepared utilizing the metaphosphate has the disadvantage that the magnesium formulation below: salts cause a setting up or solidification in the toothpaste 10 Range, percent tube. Another advantage resulting from the use of the above (1) Glycerine, 255 grams ------29-59 described compounds of cadmium, tin, zinc, manganese, (2) Water, 281 grams ------59-38 aluminum, and iron in combination with sodium meta (3) Bodying agents (50% gum karaya and 50% phosphate in fluoride dentifrices is the reduced corrosivity gum tragacanth), 14 grams ------0.5-4 towards metal containers. Prior art fluoride dentifrices may be corrosive towards metal containers such as tin The two formulations are found to yield satisfactory cans utilized to contain toothpowders, or tin, aluminum, dentifrices which possess a long shelf life without setting or lead tubes provided for the dispensing of toothpastes. up in the tube. In general, the proportion of the powder Aluminum hydrate, for example, when used in the present 20 combination compositions containing the said metal salts components is from 40% to 50% by weight in order to together with the insoluble sodium metaphosphate and obtain smooth paste. a specific fluoride exhibit less corrosivity towards the If a fluoride dentifrice is desired, a soluble fluoride above-described metal containers than do the same fluo salt, for example aluminum fluoride, is used at about ride compounds such as sodium fluoride utilized alone. 0.1%, calculated as fluoride (e.g., 0.939 in the above Specific examples illustrative of the present invention formulation). In general the weight percentage of the are set forth below. fluoride as a salt is preferred to be in the range of 0.05 Example 1 to 1%. One hundred g. of insoluble sodium metaphosphate What I claim is: were extracted with distilled water in order to remove 30 1. A dentifrice polishing composition comprising finely the soluble portion. The water extract (after separation divided insoluble sodium metaphosphate normally con from the insoluble metaphosphate) was then treated with taining calcium ion sequestering soluble phosphates and about 50 ml. of a 10% solution of zinc acetate at room a sufficient amount of a compound selected from the temperature. It was found that a filterable precipitate group consisting of cadmium halides, cadmium phos formed almost immediately, representing the zinc salts phates, cadmium sulphates, cadmium oxides, zinc halides, of short-chain polyphosphates. The insoluble sodium Zinc phosphates, zinc sulphates, zinc oxides, manganese metaphosphate was thus reduced in sequestration ability. halides, manganese phosphates, manganese sulphates, Example 2 manganese oxides, iron halides, iron phosphates, iron 40 sulphates, iron oxides, tin oxides, tin sulphates, tin phos One hundred g. of insoluble sodium metaphosphate was phates and tin halides other than fluorides, to inhibit treated with 100 ml, of distilled water in order to extract said calcium ion sequestering effect. the minor proportion of soluble components representative 2. A dentifrice polishing composition according to of shortchain polyphosphates. The water extract (after separation from the insoluble metaphosphate) was then claim 1 additionally containing from about 0.05% to treated with a 50 ml, portion of aluminum sulfate (10% about 1% by weight of a soluble fluoride selected from solution) at room temperature. It was found that a gel the group consisting of aluminum fluoride, stannous was formed which could be precipitated on heating to 60° fluoride and sodium fluoride. C. for 10 minutes. This gel, corresponding to the alumi 3. A dentifrice polishing composition comprising finely num salt of the polyphosphate components present, ren divided insoluble sodium metaphosphate containing dered the insoluble sodium metaphosphate free from a 50 water-soluble polymeric sodium phosphates, which soluble solubilizing effect on insoluble calcium salts dispersed or phosphates possess a calcium ion sequestering effect, present in the solution, and an amount of a zinc halide sufficient to inhibit the Example 3 said calcium ion sequestering effect, 5 5 4. A dentifrice polishing composition comprising finely Sequestration tests were carried out utilizing the proce divided insoluble sodium metaphosphate containing dure of Example 1 with the following compounds utilized water-soluble polymeric sodium phosphates, which solu in individual tests: cadmium chloride, stannous chloride, ble phosphates possess a calcium ion sequestering effect, Zinc sulfate, manganous sulfate, aluminum sulfate, fer and an amount of a zinc phosphate sufficient to inhibit rous chloride, and ferric sulfate. In each of these tests, 60 the said calcium ion sequestering effect. it was found that the soluble portion of the sodium meta 5. A dentifrice polishing composition as in claim 4 phosphate was precipitated to leave the remainder of the containing from 0.05% to 50% of said zinc phosphate. sodium metaphosphate free from sequestering action. 6. A dentifrice polishing composition comprising finely Example 4 divided insoluble sodium metaphosphate containing A toothpowder was prepared utilizing the following water-soluble polymeric sodium phosphates, which solu formulations by weight, and also indicating the range ble phosphates possess a calcium ion sequestering effect, of variation of the components: and an amount of zinc sulphate sufficient to inhibit the Range, percent said calcium ion sequestering effect. (1) Insoluble sodium metaphosphate, 400 grams-- 36-97 70 7. A dentifrice polishing composition comprising finely (2) Hydrated aluminum oxide (Reynolds C-33 divided insoluble sodium metaphosphate containing grade), 21 grams------1-50 water-soluble polymeric sodium phosphates, which solu (3) Detergent (sodium lauryl sulfate), 20 grams-- 2-8 ble phosphates possess a calcium ion sequestering effect, (4) Saccharine, 1 gram------0.05-2 and an amount of sufficient to inhibit said (5) Flavoring (essential oil), 4 grams------.05-2 calcium ion sequestering effect. 8,095,856 5 8. A dentifrice polishing composition comprising finely 6 divided insoluble sodium metaphosphate containing 11. A dentifrice polishing composition containing about water-soluble polymeric sodium phosphates, which solu 40% to 50% of the following components by weight: ble phosphates possess a calcium ion sequestering effect, Insoluble sodium metaphosphate containing water solPercent and an amount of zinc oxide in the range of from 0.05% 5 uble polymeric sodium phosphates which possess a A calciumcompound ion selectedsequestering from effect------the group consisting of 36-97 to 50.0% by weight relative to the said sodium meta cadmium halides, cadmium phosphates, cadmium phosphate. o Suiphates, cadmium oxides, zinc halides, zinc phos phates, zinc sulphates, zinc oxides, manganese 9. A dentifrice polishing composition containing the halides, manganese phosphates, manganese sul following components by weight: phates, manganese oxides, iron halides, iron phos Percent 0. phates, ironsulphates, iron oxides, tin oxides, tin Insoluble sodium SESEE containing water sol sulphates, tin phosphates, and tin halides other uble polymeric sodium phosphates which possess a Organicthan fluoridesdetergent ------A calciumcompound ion selected sequestering from theeffect------group consisting of 86-97 Saccharin ------cadmium halides, cadmium phosphates, cadmium Flavoring other than saccharin.------0.05-2 phates,sulphates, zinc cadmium sulphates, oxides, zinc zinc oxides,halides, manganesezinc phos in combination with an elixir comprising the following halides, manganese phosphates, manganese sul- 5 components by weight: phates, manganese oxides, iron halides, iron phos phates, ironsulphates, iron oxides, tin oxides, tin Percent sulphates, tin phosphates, and tin halides other Glycerine ------29-59 than fluorides ------50 Water ------59-38 Organic detergent ------2-8 Bodying agents selected from the group consisting of Saccharin ------0.05-2 gum karaya and gum tragacanth------0.5-4 Flavoring other than saccharia------0.05-2 20 10. A dentifrice polishing composition containing the References Cited in the file of this patent following components by Weight: UNITED STATES PATENTS Insoluble sodium metaphosphate containing water sol Percent 1,529,486 Kaemmerling et al. ------Mar. 10, 1925 luble polymeric sodium phosphates which possess a 2,086,867 Hall ------July 13, 1937 A calciumcompound ion selectedsequestering from effect.------the group consisting of 36-9. 25 2,216,821 Long ------Oct. 8, 1940 cadmium halides, cadmium phosphates, cadmium sulphates, cadmium oxides, zinc halides, zinc phos FOREIGN PATENTS hates, zinc sulphates, zinc oxides, manganese alides, manganese phosphates, manganese sul 158,717 Australia ------Sept. 9, 1954 phates, manganese oxides, iron halides, iron phos phates, ironsulphates, iron oxides, tin oxides, tin OTHER REFERENCES sulphates, tin phosphates, and tin halides other 30 than fluorides - 1-50 Chemistry of the Metal Chelate Compounds, Arthur Organic detergent - 2-8 Saccharin ------0.05-2 E. Martell et al., 1952, pages 544 and 545. Flavoring other than sacchari - 0.05-2 Cifelli: Drug and Cos. Ind., vol. 73, No. 3, September Soluble fluoride ------0.05-1 1953, pages 318, 319, 383,385, 394, 396-399.